Classifications

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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
  • C07C233/76—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by doubly-bound oxygen atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01C—PLANTING; SOWING; FERTILISING
  • A01C1/00—Apparatus, or methods of use thereof, for testing or treating seed, roots, or the like, prior to sowing or planting
  • A01C1/06—Coating or dressing seed
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
  • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
  • C07C233/81—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
  • C07C233/82—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
  • C07C233/87—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom of a carbon skeleton containing six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
  • C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
  • C07C235/46—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
  • C07C255/48—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of 2,2-dimethylcyclopropane rings, e.g. nitrile of chrysanthemumic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids
  • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
  • C07C271/24—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
  • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
  • C07D213/46—Oxygen atoms
  • C07D213/50—Ketonic radicals
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/61—Halogen atoms or nitro radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D213/81—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D263/36—One oxygen atom
  • C07D263/38—One oxygen atom attached in position 2
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

• the present invention relates to novel carboxamide compounds, a process for the preparation of these compounds and their use as nematicides.
• Carboxamides are described, for example, in WO0160783, WO03027059 and WO06016708.
• Novel carboxamides containing a cyclopropyl(hetero)aryl moiety have now been found, which show good nematicidal activity.
• the present invention thus relates to a compound of the formula I
• Y is C—H, C—F, C—Cl or N
• A1, A2, A4 and A5 are, independently of each other, N, CH or CR6, where the number of N atoms in the ring containing A1, A2, A4 and A5 is 0, 1 or 2
• R6 is, independently of each other, selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy
• R1 and R2 are each methyl, or R1 and R2 form together with the carbon atom, to which they are attached, a cyclopropyl or cyclobutyl ring
• R3 is, independently of each other, selected from halogen, cyano, R9, O—R9, NO2, COOR9, CONHR9, CONR9aR9, NHR9, NR9aR9, and NHCOR9
• R8 is, independently of
• the compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and hereinbelow, even when stereochemical details are not mentioned specifically in each case.
• the compounds of the invention may contain one or more asymmetric carbon atoms, and the compounds of formula (I) may exist as enantiomers (or as pairs of diastereoisomers) or as mixtures of such.
• the invention also covers salts and N-oxides of each compound of formula (I).
• salts of chemical compounds are in equilibrium with their corresponding non salt forms, salts share the biological utility of the non salt forms.
• salts of compounds of the invention may be useful for control of invertebrate pests and animal parasites.
• Salts amongst agriculturally and/or physiologically tolerable salts include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
• Suitable amongst agriculturally and/or physiologically tolerable salts can also be the salts of those cations which do not adversely affect the pesticidal and/or parasiticidal action of the compounds of formula (I).
• especially suitable cations are the ions of the alkali metals including sodium, potassium and lithium, of the alkaline earth metals including calcium and magnesium, and of the transition metals including manganese, copper, iron, zinc, cobalt, lead, silver, nickel, and also ammonium or organic ammonium including monoalkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium, monoalkenylammonium, dialkenylammonium, trialkenylammonium, monoalkynylammonium, dialkynylammonium, monoalkanolammonium, dialkanolammonium, C5-C6-cycloalkylammonium, piperidinium, morpholinium, pyrroli
• Alkyl groups can be in the form of a straight or branched chain and are, for example, methyl, ethyl, 1-propyl, prop-2-yl, 1-butyl, but-2-yl, or 2-methyl-prop-2-yl.
• the alkyl group (either alone or as part of a larger group, such as alkoxy-, alkylcarbonyl- or alkoxycarbonyl-), in each embodiment of the invention, is preferably C1-C3-alkyl, more preferably C1-C2-alkyl, especially methyl group.
• examples are methoxy, ethoxy, propoxy, n-butoxy, isobutoxy and also their isomeric groups; preferably, independent of other embodiments, methoxy and ethoxy, especially methoxy.
• Alkenyl groups can be in the form of straight or branched chains, and can be, where appropriate, of either the ( E )- or ( Z )-configuration. Examples are vinyl and allyl.
• the alkenyl group, in each embodiment of the invention, is preferably a C2-C3-alkenyl group, more preferably vinyl or allyl group.
• Alkynyl groups can be in the form of straight or branched chains. Examples are ethynyl and propargyl.
• the alkynyl group, in each embodiment of the invention, is preferably a C2-C3-alkynyl group, more preferably propargyl group.
• Halogen is fluorine, chlorine, bromine or iodine; halogen, in each embodiment of the invention, is fluorine, chlorine, or bromine; especially fluorine, chlorine, or bromine.
• Haloalkyl groups are alkyl groups which are substituted by one or more of the same or different halogen atoms and are, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl and 2,2,2-trifluoro-ethyl.
• the haloalkyl group (either alone or as part of a larger group, such as haloalkoxy-,), in each embodiment of the invention, is preferably trifluoromethyl and difluoromethyl.
• examples are fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2,2,2-trifluoroethoxy, 2-chloroethoxy and trifluoromethoxy.
• Cycloalkyl groups are mono-cyclic and are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
• the C3-C6-cycloalkyl group in each embodiment of the invention, is preferably a C3-C5-cycloakyl, more preferably a C3-C4-cycloalkyl group, especially a C3-cycloalkyl group.
• the cycloalkyl moiety is preferably substituted by one to four substituents, more preferably by one to three substituents, such as one or two substituents, especially by one substitutent.
• Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl; preferred are methoxycarbonyl, ethoxycarbonyl and isopropoxycarbonyl.
• Alkoxyalkyl is, for example, methoxymethyl, 2-methoxyethyl, ethoxymethyl, 2-ethoxyethyl, n-propoxymethyl, n-propoxy-2-ethyl, isopropoxymethyl and 1-isopropoxyethyl.
• the alkoxyalkyl group in each embodiment of the invention, is preferably a C1-C4-alkoxy-C1-C4-alkyl, more preferably a C1-C2-alkoxy-methyl, such as methoxymethyl and ethoxymethyl groups.
• Aryl groups are aromatic ring systems which can be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthyl, anthracenyl, indenyl or phenanthrenyl. Preferred aryl groups are phenyl and naphthyl, phenyl being most preferred.
• cycloalkylcarbonyl examples include cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl and cyclohexylcarbonyl; preferred are cyclopropylcarbonyl and cyclobutylcarbonyl.
• cycloalkoxycarbonyl examples include cyclopropyloxycarbonyl, cyclobutyloxycarbonyl, cyclopentyloxycarbonyl and cyclohexyloxycarbonyl; preferred are cyclopropyloxycarbonyl and cyclobutyloxycarbonyl.
• heteroaryl refers to aromatic ring systems containing at least one heteroatom and consisting either of a single ring or of two fused rings.
• single rings will contain up to 3 and bicyclic systems up to 5, heteroatoms, which will preferably be chosen from nitrogen, oxygen and sulphur.
• Examples of such groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, benzofuryl, benzisofuryl, benzothienyl, benzisothienyl, indolyl, isoindolyl, in
• compounds of formula (I), including a compound of formulae (IA), (IB), (IC) or (ID), can be in form of each of formula (Ia) (cis), (Ib) (trans), (1aa) (cis), (1ab) (cis), (1aa) (trans) and (1ab) (trans).
• the compounds of the formula I may occur in different tautomeric forms.
• the invention covers all those tautomeric forms and mixtures thereof.
• R1, R2, R3, R8, Y, m and p are as defined above for formula (I), and R6a, R6b, R6d and R6e are independently are, independently selected, from hydrogen, halogen, C1-C4-alkyl, and C1-C4-haloalkyl.
• a compound of formula IA is where R1, R2, R3, R8, Y, m and p are as defined above for formula (I), and R6a, R6b, R6d and R6e are, independently selected, from hydrogen, halogen, C1-C2-alkyl, and C1-C2-haloalkyl; preferably independently selected from hydrogen, difluoromethyl, trifluoromethyl, cyano and halogen; especially independently selected from hydrogen, fluoro and chloro.
• R6a is C1-C2-alkyl, or C1-C2-haloalkyl (preferably difluoromethyl or trifluoromethyl), cyano and halogen, in particular R6a is fluoro or chloro.
• a compound of formula IA is where R6a, R6b, R6d and R6e are, independently of each other, selected from hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, and halogen, Y is CH or N, R1 and R2 are each methyl, m is 0 or 1, R8, in event m is 1, is chloro, fluoro or trifluoromethyl, R3 is, independently selected from, halogen, cyano, C1-C2-alkyl, or C1-C2-haloalkyl, and p is 0, 1 or 2.
• R1, R2, R3, R8, Y, m and p are as defined above for formula (I), and R6a, R6b, and R6d are, independently selected from, hydrogen, halogen, C1-C4-alkyl, and C1-C4-haloalkyl.
• a compound of formula IB is where R1, R2, R3, R8, Y, m and p are as defined above for formula (I), and R6a, R6b, and R6d are independently selected from hydrogen, halogen, C1-C2-alkyl, C1-C2-alkoxy and C1-C2-haloalkyl; preferably independently selected from hydrogen, difluoromethyl, trifluoromethyl, cyano and halogen; especially independently selected from hydrogen, fluoro, methoxy, chloro and bromo.
• R6a is C1-C2-alkyl, or C1-C2-haloalkyl (preferably difluoromethyl or trifluoromethyl), cyano and halogen, in particular R6a is fluoro, methoxy, chloro or bromo.
• a compound of formula IB is where R1, R2, R3, R8, Y, m and p are as defined above for formula (I), and R6a, R6b, and R6d are independently selected from hydrogen, halogen, C1-C2-alkyl, and C1-C2-haloalkyl; preferably independently selected from hydrogen, difluoromethyl, trifluoromethyl, cyano and halogen; especially independently selected from hydrogen, fluoro, chloro, and bromo.
• R6a is C1-C2-alkyl, or C1-C2-haloalkyl (preferably difluoromethyl or trifluoromethyl), cyano and halogen, in particular R6a is fluoro, chloro, or bromo.
• a compound of formula IB is where R6a, R6b, and R6d are, independently of each other, selected from hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, and halogen, Y is CH or N, R1 and R2 are each methyl, m is 0 or 1, R8, in event m is 1, is chloro, fluoro or trifluoromethyl, R3 is, independently selected from, halogen, cyano, C1-C2-alkyl, or C1-C2-haloalkyl, and p is 0, 1 or 2.
• R1, R2, R3, R8, Y, m and p are as defined above for formula (I), and R6a, R6b, and R6e are, independently selected from, hydrogen, halogen, C1-C4-alkyl, C1-C3-alkoxy and C1-C4-haloalkyl.
• a compound of formula IC is where R1, R2, R3, R8, Y, m and p are as defined above for formula (I), and R6a, R6b, and R6e are, independently selected from, hydrogen, halogen, C1-C4-alkyl, and C1-C4-haloalkyl.
• a compound of formula IC is where R1, R2, R3, R8, Y, m and p are as defined above for formula (I), and R6a, R6b, and R6e are independently selected from hydrogen, halogen, C1-C2-alkyl, and C1-C2-haloalkyl; preferably independently selected from hydrogen, difluoromethyl, trifluoromethyl, cyano and halogen; especially independently selected from hydrogen, fluoro, bromo and chloro, more preferably independently selected from hydrogen, difluoromethyl, trifluoromethyl, cyano and halogen; especially independently selected from hydrogen, fluoro and chloro.
• R6e is C1-C2-alkyl, or C1-C2-haloalkyl (preferably difluoromethyl or trifluoromethyl), cyano and halogen, in particular R6e is chloro, or bromo.
• R6a is C1-C2-alkyl, or C1-C2-haloalkyl (preferably difluoromethyl or trifluoromethyl), cyano and halogen, in particular R6a is fluoro, or chloro.
• a compound of formula IC is where R6a, R6b, and R6e are, independently of each other, selected from hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, and halogen, Y is CH or N, R1 and R2 are each methyl, m is 0 or 1, R8, in event m is 1, is chloro, fluoro or trifluoromethyl, R3 is, independently selected from, halogen, cyano, C1-C2-alkyl, or C1-C2-haloalkyl, and p is 0, 1 or 2.
• Y is CH or N; more preferably Y is CH.
• R1 and R2 are each methyl or together with the carbon atom, to which they are attached, is a cyclopropyl or cyclobutyl ring; more preferably, in an embodiment of formula (I), including each of formulae (IA), (IB), and (IC), independent of other embodiments, R1 and R2 are each methyl or together with the carbon atom, to which they are attached, is a cyclopropyl ring; even more preferably R1 and R2 are each methyl.
• R8 is, independently selected from, a halogen, cyano, C1-C2-alkyl, or C1-C2-haloalkyl; more preferably, R8 is, independently selected from, fluoro, chloro or trifluoromethyl.
• R8 is preferably in a position ortho to the carbonyl group; and is preferably fluorine.
• each R6, including R6a, R6b, R6c, R6d and R6e is independently selected, from hydrogen, halogen, C1-C2-alkyl, C1-C2-alkoxy and C1-C2-haloalkyl;
• R9 and R9a are preferably selected from C1-C4-alkyl, which is optionally substituted by one ore more R10, wherein R10 is, independently selected from a halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy.
• R3 is independently selected from a halogen, cyano, C1-C2-alkyl, C1-C2-haloalkyl, and a phenyl substituted with one or more of, independently selected from, C1-C4-haloalkyl, C1-C4-haloalkoxy, and halogen; preferably R3 is independently selected from halogen, cyano, C1-C2-alkyl, C1-C2-haloalkyl; more preferably R3 is independently selected from chloro, fluoro and trifluoromethyl.
• R3 is a phenyl, the one or more substituents on phenyl are preferably, independently selected, from chloro and fluoro.
• p is 2, 3 or 4 and each of R3 are the same.
• p is 0, 1 or 2; more preferably 1.
• m is 0, 1 or 2, more preferably m is 0 or 1, especially m is 0.
• the ring is 2,6-difluorophenyl (G1), 3-trifluoromethyl-2-pyridyl (G4), 3-chloro-2-pyridyl (G5), 2-trifluoromethyl-3-pyridyl (G6), 2-chloro-3-pyridyl (G7), 3-fluoro-2-pyridyl (G8), 3-chloro-2-pyrazinyl (G9), or 3-bromo-2-pyridyl (G13); advantageously the ring is 2,6-difluorophenyl (G1), 3-trifluoromethyl-2-pyridyl (G4), 3-chloro-2-pyridyl (G5), 2-trifluoromethyl-3-pyridyl (G6), 2-chloro-3-pyridyl (G7), 3-fluoro-2-pyridyl (G8), or 3-bromo-2-pyridyl (G13).
• the ring is 2,6-
• preferred examples of the ring containing A1, A2, A4 and A5 are 2,6-difluorophenyl (G1), 2-trifluoromethyl-phenyl (G2), 2-fluorophenyl (G3), 3-trifluoromethyl-2-pyridyl (G4), 3-chloro-2-pyridyl (G5), 2-trifluoromethyl-3-pyridyl (G6), 2-chloro-3-pyridyl (G7), 3-fluoro-2-pyridyl (G8), 3-chloro-2-pyrazinyl (G9), 3-methyl-2-pyrazinyl (G10), 3-bromo-2-pyrazinyl (G11) and 3-trifluoromethyl-2-pyrazinyl (G12).
• the ring is 2,6-difluorophenyl (G1), 3-chloro-2-pyridyl (G5), 2-trifluoromethyl-3-pyridyl (G6), 2-chloro-3-pyridyl (G7), 3-fluoro-2-pyridyl (G8), 3-chloro-2-pyrazinyl (G9), 3-methyl-2-pyrazinyl (G10) or 3-bromo-2-pyrazinyl (G11); advantageously the ring is 2,6-difluorophenyl (G1), 3-chloro-2-pyridyl (G5), 2-trifluoromethyl-3-pyridyl (G6), 2-chloro-3-pyridyl (G7), 3-fluoro-2-pyridyl (G8), 3-chloro-2-pyrazinyl (G9) or 3-methyl-2-pyrazinyl (G10).
• the ring is 2,6-difluorophenyl (G
• Y is CH or N
• R1 and R2 are each methyl or together with the carbon atom, to which they are attached, a cyclopropyl or cyclobutyl ring
• p is 0, 1 or 2
• each R3 is independently selected from halogen and C1-C2-haloalkyl
• m is 0 or 1
• R8 is a halogen
• the ring containing A1, A2, A4 and A5 is selected from 2,6-difluorophenyl (G1), 3-trifluoromethyl-2-pyridyl (G4), 3-chloro-2-pyridyl (G5), 2-trifluoromethyl-3-pyridyl (G6), 2-chloro-3-pyridyl (G7), 3-fluoro-2-pyridyl (G8), or 3-bromo-2-pyridyl (G13).
• Y is CH or N
• R1 and R2 are each methyl or together with the carbon atom, to which they are attached, a cyclopropyl ring
• p is 0, 1 or 2
• each R3 is independently selected from halogen and C1-C2-haloalkyl
• m is 0 or 1
• R8 is a halogen
• the ring containing A1, A2, A4 and A5 is selected from 2,6-difluorophenyl (G1), 3-chloro-2-pyridyl (G5), 2-trifluoromethyl-3-pyridyl (G6) or 2-chloro-3-pyridyl (G7).
• Compounds of formula I may be prepared according to Scheme 1 by acylation of an organometallic compound of formula III in which R3, p, R8, m and Y are as defined under formula I, and M(a) is a metal for instance an alkali metal such as lithium or an alkaline earth metal halogenide for instance magnesium chloride or magnesium bromide, with a carboxylic acid derivative of formula II in which A1, A2, A4, A5, R1 and R2 are as defined under formula I, and X(a) is a C1-C6 alkoxy, a hetero-substituted —C1-C6 alkoxy or a heteroatom-substituted dialkylaminyl, preferably an N,O-dimethylhydroxyaminyl or a morpholinyl, and generally in a solvent, such as methylene chloride, chloroform, toluene, DMF, but preferably THF, for between 10 minutes and 5 hours, preferably 30 min to 2 hours, and between
• X(a)H is for instance a C1-C6 alkanol, a heteroatom-substituted C1-C6 alcohol, a heteroatom-substituted dialkyl amine or a salt thereof, preferably N,O-dimethylhydroxylamine hydrochloride or morpholine in a solvent, such as methylene chloride, chloroform, toluene, DMF, dimethylacetamide, NMP, but preferably methylene chloride, in presence of a base, for between 1 day and two weeks, preferably 1 day to one week, and between 0° C. to 30° C., preferably 20° C. to 25° C.
• Typical bases used are pyridine and triethylamine.
• A1, A2, A4 and A5 are, independently of each other, N, CH or CR6, where the number of N atoms in the ring containing A1, A2, A4 and A5 is 0, 1 or 2, R6 is, independently of each other, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, or C1-C4-haloalkoxy and R1 and R2 are as defined for formula (I); provided when A1 is CH or C—CH3, at least one of A4 and A5 is N or CR6.
• These compounds of the formula IIc are novel and are also part of the present invention.
• One group of compounds of the formula IV are those of the formula IVa
• A1, A2, A4 and A5 are, independently of each other, N, CH or CR6, where the number of N atoms in the ring containing A1, A2, A4 and A5 is 0, 1 or 2, R6 is, independently of each other, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, or C1-C4-haloalkoxy, and R1 and R2 are as defined for formula (I); provided when A1 is CH or C—C1-C4-alkyl, at least one of A2, A4 and A5 is N or CR6.
• a compound of formula (IVa) is where A1 is N or CR6, A2, A4 and A5 are, independently of each other, N, CH or CR6, where the number of N atoms in the ring containing A1, A2, A4 and A5 is 0, 1 or 2, R6 is, independently of each other, hydrogen, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy, R6 is halogen, cyano, C1-4haloalkyl, C1-4alkoxy, or C1-4haloalkoxy, and R1 and R2 are as defined for formula (I).
• a compound of formula (IVa) is where A1, A2, A4 and A5 are, independently of each other, N, CH or CR6, where the number of N atoms in the ring containing A1, A2, A4 and A5 is 0, 1 or 2, R6 is, independently of each other, halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, or C1-C4-haloalkoxy, and R1 and R2 are as defined for formula (I); provided when A1 is CH or C—C1-C4-alkyl, at least one of A2, A4 and A5 is N.
• Typical examples of an organoalkaline is n-butyl lithium or phenyl lithium.
• Typical examples of an organoalkaline earth reagents is isopropyl magnesium chloride, in the absence or in the presence of LiCl (“turbo-Grignard”).
• Typical examples of an alkaline earth metal is magnesium, which can be activated with various reagents including iodine.
• Compounds of Formula V are either commercially available or can be synthesized by known methods. One such method is shown below in scheme 4.
• Compounds of the formula V can be prepared by cyclopropanation of a phenyl or pyridyl alkene of the formula VI, in which R8, m, and R3 are as defined under formula R1 and q is 0-2.
• the reagent used for the cyclopropanation is a carbenoid of the formula XIII, in which R3 is as defined under formula I, r is 0-2, and Mc is a metal or metal salt, which can be ligated with ligands.
• the reagent XIII can be prepared and used stochiometrically or it can be generated in situ or in nascendi from a carbene precursor and a metal, or metal salt which can be ligated with ligands,
• the metal or metal salt can be used catalytically.
• Metals, the salts and complexes of which are often used for this purpose are Fe, Rh, Co and Ru.
• Carbene precursors are typically dihaloalkanes or diazo compounds, or precursors of these. Such methods are described in H. M. W. Davies Organic Reactions 2001, 1. An alternative method is the Simmons-Smith reaction using organozinc compounds instead of XIII is described in A. B. Charette et al. Organic Reactions 2001, 58, 1.
• the trifluoromethyldiazomethane is generated by treatment of a salt of 2,2,2-trifluoroethylamine with sodium nitrite in aqueous solution.
• This process is described in Angew. Chem. Int. Ed. 2010, 49, 938 and JP2011/105691. However this process is only described for amounts less than 1 g. It has been found that scaling this process up to 1 g or more results in an unacceptable rise in temperature. Furthermore the large volumes are a disadvantage. It has now been found that controlled addition of a sodium nitrite solution to a solution of a salt of 2,2,2-trifluoroethylamine in the presence of a metal catalyst allows for a safer controlled exotherm and a higher volume yield.
• External cooling can be used to remove heat of reaction thus allowing a faster process.
• the reaction only takes place once the nitrite solution is added.
• This temperature range is preferably between 0° C. and 100° C., more preferably between 0° C. and 50° C., most preferably between 10° C. and 40° C.
• the addition can be controlled by adding the nitrite solution at a particular rate or by adding the nitrite solution in portions, or by a combination of both. This process is superior and novel and part of the present invention. Many metal catalysts described in H. M. W. Davies Organic Reactions 2001, 1 can be used for this process.
• Fe, Co, and Ru salts and complexes are preferred. More preferred are Fe complexes. Most preferred is Fe(TPP)Xd in which TPP is tetraphenylporphorin and Xd is a halide, carboxylate, or sulfonate group. More preferably Xd is a halide particularly chloride.
• Compounds of formula I may be prepared according to Scheme 5 by oxidation of an alcohol of formula VII, in which A1, A2, A4, A5, R 1 , R 2 , Y, R3, p, R8 and m are as defined under formula I, with an oxidation reagent.
• Typical reagents for such type of transformation are chromium based oxidation reagents such as Collins reagent, Jones reagent, pyridinium chlorochromate, pyridinium dichromate, manganese based oxidation reagents such as MnO 2 and KMnO 4 , periodinane based oxidation reagents such as Dess-Martin periodinane as described in D. L. Boger, Modern Organic Synthesis, TSRI Press, La Jolla Calif., 1999 pp. 87-93.
• Aldehydes of formula VIII in which A1, A2, A4, A5, R 1 and R 2 are as defined under formula I may be prepared according to Scheme 7 by oxidation of an alcohol of formula IX, in which A1, A2, A4, A5, R 1 , and R 2 are as defined under formula I, with an oxidation reagent.
• Typical reagents for such type of transformation are chromium based oxidation reagents such as Collins reagent, Jones reagent, pyridinium chlorochromate, pyridinium dichromate, manganese based oxidation reagents such as MnO 2 and KMnO 4 , ruthenium based oxidation reagents such as TPAP, periodinane based oxidation reagents such as Dess-Martin periodinane or by using Swern or Moffat-Pfitzner oxidation as described in D. L. Boger, Modern Organic Synthesis, TSRI Press, La Jolla Calif., 1999 pp. 87-93.
• Compounds of formula IXa in which A1, A2, A4, A5, R 1 , R 2 , are as defined under formula I, may be prepared according to Scheme 8 by ring-opening reduction of an azlactone of formula IV, in which A1, A2, A4, A5, R 1 , R 2 are as defined under formula I, with a reducing reagent.
• Reducing agents which can be used are for example aluminium hydride reducing agents such as lithium aluminium hydride (LiAlH4), diisobutylaluminium hydride (DIBALH), borohydride reducing agents, for instance sodium borohydride (NaBH4), lithium borohydride (LiBH4) as listed in D. L.
• Compounds of formula I may be prepared according to Scheme 10 by reacting via a cross-coupling reaction a compound of formula XI in which A1, A2, A4, A5, R 1 , R 2 , Y, R8 and m are as defined under formula I and X(c) is a leaving group selected from halogen, preferably chloro and bromo, or triflate, mesylate or tosylate, with a cyclopropyl donor of formula XII in which R3 and p is as defined under formula I, and Mb is a functionalized metal or metalloid, for example a boronate, a boronic acid, a boronic ester such as a pinacol ester, a trifluoroborate, in a presence of a transition metal-based catalyst, for example a palladium based catalyst and a base.
• Cyclopropylation agent of formula XII are either commercially available or can be prepared according to procedure described for example in Tetrahedron Lett. 2002, 43, 6987, in Tetrahedron Lett. 2010, 51, 1009, in J. Org. Chem. 2010, 75, 6677.
• Other cross coupling reaction such as Stille and Negishi are possible when M(b) is for example a Bu 3 Sn, ZnCl, or ZnBr.
• A1, A2, A4 and A5 are as defined under formula I, and X(c) is halogen, hydroxy or C 1-6 alkoxy, preferably chloro, in the presence of a base, such as triethylamine, Hunig base, sodium bicarbonate, sodium carbonate, potassium carbonate, pyridine or quinoline, but preferably triethylamine, and in a solvent, such as diethylether, TBME, THF, dichloromethane, chloroform, DMF or NMP, for between 10 minutes and 48 hours, preferably 12 to 24 hours, and between 0° C. and reflux, preferably 20 to 25° C.
• a base such as triethylamine, Hunig base, sodium bicarbonate, sodium carbonate, potassium carbonate, pyridine or quinoline, but preferably triethylamine
• a solvent such as diethylether, TBME, THF, dichloromethane, chloroform, DMF or NMP, for between 10 minutes and 48
• a coupling agent such as benzotriazol-1-yloxytris(dimethylamino)phosphoniumhexafluorophosphate, bis-(2-oxo-3-oxazolidinyl)-phosphinic acid chloride (BOP—Cl), N,N′-dicyclohexylcarbodiimide (DCC) or 1,1′-carbonyl-diimidazole (CD), may be used.
• BOP—Cl bis-(2-oxo-3-oxazolidinyl)-phosphinic acid chloride
• DCC N,N′-dicyclohexylcarbodiimide
• CD 1,1′-carbonyl-diimidazole
• the reactants can be reacted in the presence of a base.
• suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
• Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
• DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
• the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents.
• the reaction is advantageously carried out in a temperature range from approximately ⁇ 80° C. to approximately +140° C., preferably from approximately ⁇ 30° C. to approximately +100° C., in many cases in the range between ambient temperature and approximately +80° C.
• a compound of formula (I) can be converted in a manner known per se into another compound of formula (I) by replacing one or more substituents of the starting compound of formula (I) in the customary manner by (an)other substituent(s) according to the invention.
• Salts of compounds of formula (I) can be prepared in a manner known per se.
• acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
• a salt is chosen depending on its tolerances for compound's use, such as agricultural or physiological tolerance.
• Salts of compounds of formula (I) can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
• Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
• a salt of inorganic acid such as hydrochloride
• a suitable metal salt such as a sodium, barium or silver salt
• the compounds of formula (I), which have salt-forming properties can be obtained in free form or in the form of salts.
• Diastereomer mixtures or racemate mixtures of compounds of formula (I), in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
• Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl celulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphoric, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give
• Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.
• N-oxides can be prepared by reacting a compound of the formula (I) with a suitable oxidizing agent, for example the H 2 O 2 /urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
• a suitable oxidizing agent for example the H 2 O 2 /urea adduct
• an acid anhydride e.g. trifluoroacetic anhydride
• the compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
• Table 1 individualises 29 compounds of formula (ID) wherein for each row of Table Y, the A substituent is as defined in Table 1; similarly, Table 2 individualises 29 compounds of formula (ID) wherein for each row of Table Y, the A substituent is as defined in Table 2; and so on for Tables 3 to 18.
• Table 1 provides 29 compounds of formula (ID), wherein A is
• compound 1.001 has the following structure:
• Table 2 provides 29 compounds of formula (ID) wherein A is 2-trifluoromethyl-phenyl (G2) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 3 provides 29 compounds of formula (ID) wherein A is 2-fluorophenyl (G3) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 4 provides 29 compounds of formula (ID) wherein A is 3-trifluoromethyl-2-pyridyl (G4) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 5 provides 29 compounds of formula (ID) wherein A is 3-chloro-2-pyridyl (G5) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 6 provides 29 compounds of formula (ID) wherein A is 2-trifluoromethyl-3-pyridyl (G6) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 7 provides 29 compounds of formula (ID) wherein A is 2-chloro-3-pyridyl (G7) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 8 provides 29 compounds of formula (ID) wherein A is 3-fluoro-2-pyridyl (G8) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 9 provides 29 compounds of formula (ID) wherein A is 3-chloro-2-pyrazinyl (G9) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 10 provides 29 compounds of formula (ID) wherein A is 3-methyl-2-pyrazinyl (G10) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 11 provides 29 compounds of formula (ID) wherein A is 3-bromo-2-pyrazinyl (G11) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 12 provides 29 compounds of formula (ID) wherein A is 3-trifluoromethyl-2-pyrazinyl (G12) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 13 provides 29 compounds of formula (ID) wherein A is 3-bromo-2-pyridyl (G13) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 14 provides 29 compounds of formula (ID) wherein A is 2-bromo-3-pyridyl (G14) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 15 provides 29 compounds of formula (ID) wherein A is 3-methyl-2-pyridyl (G15) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 16 provides 29 compounds of formula (ID) wherein A is 3-methoxy-2-pyridyl (G16) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 17 provides 29 compounds of formula (ID) wherein A is o-tolyl (G17) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• Table 18 provides 29 compounds of formula (ID) wherein A is 2-chlorophenyl (G18) and Y, R1, R2, R3a and R8a are as defined in each row of Table Y.
• a compound of formula (I) has been found to control the damage caused by a pest and/or fungi.
• a compound of formula (I) can be used in agriculture.
• the invention is moreover directed to a method of controlling damage and/or yield loss caused by a pest and/or fungi which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest and/or fungi or to a plant propagation material an effective amount of a compound of formula (I).
• the compounds according to the invention can be used for controlling, i. e. containing or destroying, pests and/or fungi which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers, seeds or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
• the compounds of formula (I) according to the invention are preventively and/or curatively valuable active ingredients in the field of pest control, even at low rates of application, which can be used against pesticide resistant pests and fungi, which compounds of formula (I) have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.
• the compounds according to the invention may act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina.
• the insecticidal or acaricidal activity of the compounds according to the invention can manifest itself directly, i. e. in destruction of the pests, which takes place either immediately or only after some time has elapsed, for example during ecdysis, or indirectly, for example in a reduced oviposition and/or hatching rate, a good activity corresponding to a destruction rate (mortality) of at least 50 to 60%.
• the compounds of formula I according to the invention have, for practical purposes, a very advantageous spectrum of activities for protecting animals and useful plants against attack and damage by nematodes. Accordingly, the present invention also makes available a nematicidal composition comprising compounds of the invention, such as formula (I).
• the invention also relates to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii , and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Endoparasitic-, Semiendoparasitic- and Ectoparasitic nema
• the nematode species Meloidogyne spp., Heterodera spp., Rotylenchus spp. and Pratylenchus spp. can be controlled by compounds of the invention.
• animal pests are:
• the invention may also relate to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula (I) is applied as active ingredient to the plants, to parts thereof or the locus thereof.
• the compounds of formula (I) according to the invention are distinguished by activity, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous useful plants.
• the compounds of formula (I) can be used to inhibit or destroy the diseases that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
• compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
• fungi examples include: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria ); Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia ); the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula ); Oomycetes classes (e.g.
• Phytophthora, Pythium, Plasmopara Zygomycetes (e.g., Rhizopus spp.); family Phakopsoraceae, particularly those of the genus Phakopsora , for example Phakopsora pachyrhizi , which is also referred to as Asian soybean rust, and those of the family Pucciniaceae, particularly those of the genus Puccinia such as Puccinia graminis , also known as stem rust or black rust, which is a problem disease in cereal plants and Puccinia recondita , also known as brown rust.
• family Phakopsoraceae particularly those of the genus Phakopsora , for example Phakopsora pachyrhizi , which is also referred to as Asian soybean rust
• Pucciniaceae particularly those of the genus Puccinia
• Puccinia graminis also known as stem rust or black rust, which
• the fungicide composition according to the present invention may also be used against fungal diseases liable to grow on or inside timber.
• the term “timber” means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood.
• the method for treating timber according to the invention mainly consists in contacting one or more compounds of the present invention, or a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means.
• Compounds of this invention are effective for controlling nematode, insect, acarid pests and/or fungal pathogens of agronomic plants, both growing and harvested, when employed alone, they may also be used in combination with other biological active agents used in agriculture, such as one or more nematicides, insecticides, acaricides, fungicides, bactericides, plant activator, molluscicide, and pheromones (whether chemical or biological). Mixing the compounds of the invention or the compositions thereof in the use form as pesticides with other pesticides frequently results in a broader pesticidal spectrum of action.
• formula (I) compounds of this invention may be used effectively in conjunction or combination with pyrethroids, neonicotinoids, macrolides, diamides, phosphates, carbamates, cyclodienes, formamidines, phenol tin compounds, chlorinated hydrocarbons, benzoylphenyl ureas, pyrroles and the like.
• compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding, for example, one or more insecticidally, acaricidally, nematicidally and/or fungicidally active agents.
• the combinations compounds of formula (I) with other insecticidally, acaricidally, nematicidally and/or fungicidally active agents may also have further surprising advantages which can also be described, in a wider sense, as synergistic activity. For example, better tolerance by plants, reduced phytotoxicity, pests or fungi can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
• TX means “one compound selected from the 29 compounds of each of Tables 1 to 18 shown above, more preferably Tables 19 and 20 shown below, even more preferably on compound selected from 19.001, 19.003, 19.004, 19.005, 19.006, 19.007, 19.008, 19.009, 19.010, 19.011, 19.012, 19.013, 19.014, 19.015, 19.017, 19.018, 19.019, 19.020, 19.021, 19.022, 19.023, 19.024, 19.025, 19.026, 19.027, 19.028, 19.029, 19.033, 19.036, 19.037, 19.038, 19.041, 19.042, 19.043, 19.044, 19.045, 19.046, 19.053, 19.054, 19.056, 19.057, 19.059, 19.060, 19.062 and 19.064”):
• an adjuvant selected from the group of substances consisting of petroleum oils (alternative name) (628)+TX,
• an acaricide selected from the group of substances consisting of 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910)+TX, 2,4-dichlorophenyl benzenesulfonate (IUPAC/Chemical Abstracts name) (1059)+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295)+TX, 4-chlorophenyl phenyl sulfone (IUPAC name) (981)+TX, abamectin (1)+TX, acequinocyl (3)+TX, acetoprole [CCN]+TX, acrinathrin (9)+TX, aldicarb (16)+TX, aldoxycarb (863)+TX, alpha-cypermethrin (202)+TX, amidithion (870)+TX, amidoflumet [CCN]+TX, amid
• an algicide selected from the group of substances consisting of bethoxazin [CCN]+TX, copper dioctanoate (IUPAC name) (170)+TX, copper sulfate (172)+TX, cybutryne [CCN]+TX, dichlone (1052)+TX, dichlorophen (232)+TX, endothal (295)+TX, fentin (347)+TX, hydrated lime [CCN]+TX, nabam (566)+TX, quinoclamine (714)+TX, quinonamid (1379)+TX, simazine (730)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX,
• an anthelmintic selected from the group of substances consisting of abamectin (1)+TX, crufomate (1011)+TX, doramectin (alternative name) [CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin (alternative name) [CCN]+TX, ivermectin (alternative name) [CCN]+TX, milbemycin oxime (alternative name) [CCN]+TX, moxidectin (alternative name) [CCN]+TX, piperazine [CCN]+TX, selamectin (alternative name) [CCN]+TX, spinosad (737) and thiophanate (1435)+TX,
• an avicide selected from the group of substances consisting of chloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX,
• a bactericide selected from the group of substances consisting of 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222)+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX, 8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, copper dioctanoate (IUPAC name) (170)+TX, copper hydroxide (IUPAC name) (169)+TX, cresol [CCN]+TX, dichlorophen (232)+TX, dipyrithione (1105)+TX, dodicin (1112)+TX, fenaminosulf (1144)+TX, formaldehyde (404)+TX, hydrargaphen (alternative name) [CCN]+TX, kasugamycin (483)+TX, kasugamycin hydrochloride hydrate (483)+TX, nickel bis(
• a biological agent selected from the group of substances consisting of Adoxophyes orana GV (alternative name) (12)+TX, Agrobacterium radiobacter (alternative name) (13)+TX, Amblyseius spp. (alternative name) (19)+TX, Anagrapha falcifera NPV (alternative name) (28)+TX, Anagrus atomus (alternative name) (29)+TX, Aphelinus abdominalis (alternative name) (33)+TX, Aphidius colemani (alternative name) (34)+TX, Aphidoletes aphidimyza (alternative name) (35)+TX, Autographa californica NPV (alternative name) (38)+TX, Bacillus firmus (alternative name) (48)+TX, Bacillus sphaericus Neide (scientific name) (49)+TX, Bacillus thuringiensis Hopkins (scientific name) (5
• a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537)+TX,
• a chemosterilant selected from the group of substances consisting of apholate [CCN]+TX, bisazir (alternative name) [CCN]+TX, busulfan (alternative name) [CCN]+TX, diflubenzuron (250)+TX, dimatif (alternative name) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa [CCN]+TX, methiotepa [CCN]+TX, methyl apholate [CCN]+TX, morzid [CCN]+TX, penfluron (alternative name) [CCN]+TX, tepa [CCN]+TX, thiohempa (alternative name) [CCN]+TX, thiotepa (alternative name) [CCN]+TX, tretamine (alternative name) [CCN] and
• an insect pheromone selected from the group of substances consisting of (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol (IUPAC name) (222)+TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829)+TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541)+TX, (E,Z)-tetradeca-4,10-dien-1-yl acetate (IUPAC name) (779)+TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285)+TX, (Z)-hexadec-11-enal (IUPAC name) (436)+TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name) (437)+TX, (Z)-hexadec-13-en-11-yn-1-y
• an insect repellent selected from the group of substances consisting of 2-(octylthio)-ethanol (IUPAC name) (591)+TX, butopyronoxyl (933)+TX, butoxy(polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC name) (1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC name) (1048)+TX, diethyltoluamide [CCN]+TX, dimethyl carbate [CCN]+TX, dimethyl phthalate [CCN]+TX, ethyl hexanediol (1137)+TX, hexamide [CCN]+TX, methoquin-butyl (1276)+TX, methylneodecanamide [CCN]+TX, oxamate [CCN] and picaridin [CCN]+TX,
• an insecticide selected from the group of substances consisting of 1-dichloro-1-nitroethane (IUPAC/Chemical Abstracts name) (1058)+TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane (IUPAC name) (1056), +TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX, 1-bromo-2-chloroethane (IUPAC/Chemical Abstracts name) (916)+TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451)+TX, 2,2-dichlorovinyl 2-ethylsulphinylethyl methyl phosphate (IUPAC name) (1066)+TX, 2-(1,3-dith
• a molluscicide selected from the group of substances consisting of bis(tributyltin) oxide (IUPAC name) (913)+TX, bromoacetamide [CCN]+TX, calcium arsenate [CCN]+TX, cloethocarb (999)+TX, copper acetoarsenite [CCN]+TX, copper sulfate (172)+TX, fentin (347)+TX, ferric phosphate (IUPAC name) (352)+TX, metaldehyde (518)+TX, methiocarb (530)+TX, niclosamide (576)+TX, niclosamide-olamine (576)+TX, pentachlorophenol (623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+T
• a nematicide selected from the group of substances consisting of AKD-3088 (compound code)+TX, 1,2-dibromo-3-chloropropane (IUPAC/Chemical Abstracts name) (1045)+TX, 1,2-dichloropropane (IUPAC/Chemical Abstracts name) (1062)+TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063)+TX, 1,3-dichloropropene (233)+TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC/Chemical Abstracts name) (1065)+TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980)+TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286)+TX, 6-isopentenylaminopur
• a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX,
• a plant activator selected from the group of substances consisting of acibenzolar (6)+TX, acibenzolar-S-methyl (6)+TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720)+TX,
• a rodenticide selected from the group of substances consisting of 2-isovalerylindan-1,3-dione (IUPAC name) (1246)+TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748)+TX, alpha-chlorohydrin [CCN]+TX, aluminium phosphide (640)+TX, antu (880)+TX, arsenous oxide (882)+TX, barium carbonate (891)+TX, bisthiosemi (912)+TX, brodifacoum (89)+TX, bromadiolone (91)+TX, bromethalin (92)+TX, calcium cyanide (444)+TX, chloralose (127)+TX, chlorophacinone (140)+TX, cholecalciferol (alternative name) (850)+TX, coumachlor (1004)+TX, coumafuryl (
• a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)-ethyl piperonylate (IUPAC name) (934)+TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903)+TX, farnesol with nerolidol (alternative name) (324)+TX, MB-599 (development code) (498)+TX, MGK 264 (development code) (296)+TX, piperonyl butoxide (649)+TX, piprotal (1343)+TX, propyl isomer (1358)+TX, S421 (development code) (724)+TX, sesamex (1393)+TX, sesasmolin (1394) and sulfoxide (1406)+TX,
• an animal repellent selected from the group of substances consisting of anthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX, copper oxychloride (171)+TX, diazinon (227)+TX, dicyclopentadiene (chemical name) (1069)+TX, guazatine (422)+TX, guazatine acetates (422)+TX, methiocarb (530)+TX, pyridin-4-amine (IUPAC name) (23)+TX, thiram (804)+TX, trimethacarb (840)+TX, zinc naphthenate [CCN] and ziram (856)+TX,
• a virucide selected from the group of substances consisting of imanin (alternative name) [CCN] and ribavirin (alternative name) [CCN]+TX,
• a wound protectant selected from the group of substances consisting of mercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl (802)+TX,
• azaconazole 60207-31-0]+TX, bitertanol [70585-36-3]+TX, bromuconazole [116255-48-2]+TX, cyproconazole [94361-06-5]+TX, difenoconazole [119446-68-3]+TX, diniconazole [83657-24-3]+TX, epoxiconazole [106325-08-0]+TX, fenbuconazole [114369-43-6]+TX, fluquinconazole [136426-54-5]+TX, flusilazole [85509-19-9]+TX, flutriafol [76674-21-0]+TX, hexaconazole [79983-71-4]+TX, imazalil [35554-44-0]+TX, imibenconazole [86598-92-7]+TX, i
• the mass ratio of any two ingredients in each combination is selected as to give the desired, for example, synergistic action. In general, the mass ratio would vary depending on the specific ingredient and how many ingredients are present in the combination. Generally, the mass ratio between any two ingredients in any combination of the present invention, independently of one another, is from 100:1 to 1:100, including from 99:1, 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90:10, 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34, 65:45, 64:46, 63:47, 62
• Preferred mass ratios between any two components of present invention are from 75:1 to 1:75, more preferably, 50:1 to 1.50, especially 25:1 to 1:25, advantageously 10:1 to 1:10, such as 5:1 to 1:5, for example 1:3 to 3:1.
• the mixing ratios are understood to include, on the one hand, ratios by mass and also, on other hand, molar ratios.
• Examples of application methods for the compounds of the invention and compositions thereof, that is the methods of controlling pests/fungi in the agriculture, are spraying, atomizing, dusting, brushing on, dressing, scattering or pouring—which are to be selected to suit the intended aims of the prevailing circumstances.
• a preferred method of application in agriculture is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest/fungi in question.
• the active ingredient can reach the plants via the root system (systemic action), by applying the compound to the locus of the plants, for example by application of a liquid composition of the compound into the soil (by drenching), or by applying a solid form of the compound in the form of granules to the soil (soil application).
• granules can be metered into the flooded paddy-field.
• Typical rates of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha, such as 50 to 300 g/ha.
• the compounds of the invention and compositions thereof are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
• the propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing.
• the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
• These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention.
• Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
• seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
• the present invention also comprises seeds coated or treated with or containing a compound of formula I.
• coated or treated with and/or containing generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application.
• the seed product When the said seed product is (re)planted, it may absorb the active ingredient.
• the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I).
• Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
• the seed treatment application of the compound formula I can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
• Suitable target plants are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soya; oil plants, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts,
• the plant is selected from cereals, corn, soybean, rice, sugarcane, vegetables and oil plants.
• plant is to be understood as including also plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
• Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae ; or insecticidal proteins from Bacillus thuringiensis , such as ⁇ -endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Viol, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
• insecticidal proteins from Bacillus cereus or Bacillus popilliae or insecticidal proteins from Bacillus thuringiensis , such as ⁇ -endotoxins, e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab
• Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus ; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ec
• ⁇ -endotoxins for example Cry1Ab, Cry1Ac, Cry1F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
• Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701).
• Truncated toxins for example a truncated Cry1Ab, are known.
• modified toxins one or more amino acids of the naturally occurring toxin are replaced.
• amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
• Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
• the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
• insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
• Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresse
• transgenic plants are:
• This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence.
• the preparation of such transgenic maize plants is described in WO 03/018810.
• MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9.
• MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5.
• NK603 ⁇ MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
• CP4 EPSPS obtained from Agrobacterium sp. strain CP4
• Roundup® contains glyphosate
• Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
• a compound of the present invention is used in the form of a composition (e.g. formulation) containing a carrier.
• a compound of the invention and compositions thereof can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure), gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra low volume (ulv) liquid, ultra low volume (ulv) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water
• a formulation typically comprises a liquid or solid carrier and optionally one or more customary formulation auxiliaries, which may be solid or liquid auxiliaries, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, clays, inorganic compounds, viscosity regulators, surfactant, binders and/or tackifiers.
• auxiliaries for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, clays, inorganic compounds, viscosity regulators, surfactant, binders and/or tackifiers.
• composition may also further comprise a fertilizer, a micronutrient donor or other preparations which influence the growth of plants as well as comprising a combination containing the compound of the invention with one or more other biologically active agents, such as bactericides, fungicides, nematocides, plant activators, acaricides, and insecticides.
• a fertilizer such as bactericides, fungicides, nematocides, plant activators, acaricides, and insecticides.
• the present invention also makes available a composition
• a composition comprising a compound of the invention and an agronomically carrier and optionally one or more customary formulation auxiliaries.
• compositions are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid compound of the present invention and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the compound of the present invention with the auxiliary (auxiliaries).
• auxiliaries for example by grinding, screening and/or compressing a solid compound of the present invention
• at least one auxiliary for example by intimately mixing and/or grinding the compound of the present invention with the auxiliary (auxiliaries).
• the grinding/milling of the compounds is to ensure specific particle size.
• compositions for use in agriculture are emulsifiable concentrates, suspension concentrates, microemulsions, oil dispersibles, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise—at least—a compound according to the invention and the type of composition is to be selected to suit the intended aims and the prevailing circumstances.
• suitable liquid carriers are unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C 8 to C 12 of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unexpodized or ep
• solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
• ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
• highly disperse silicas or highly disperse absorbtive polymers are also possible to add highly disperse silicas or highly disperse absorbtive polymers.
• Suitable particulate adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are calcite or sand.
• a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.
• Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties.
• the surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature.
• Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols.
• water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups.
• the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit.
• nonylphenoxypolyethoxyethanol castor oil polyglycol ether, polypropylene glycol/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol.
• fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate.
• the cationic surfactants are, especially, quarternary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 C atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals.
• the salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethylammonium bromide.
• Suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface-active compounds.
• suitable soaps are the alkali, alkaline earth or (unsubstituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 C atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates.
• synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.
• the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl radical of approximately 8 to approximately 22 C atoms, alkyl also to be understood as including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulphuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulphuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.
• the sulfonated benzimidazole derivatives preferably contain 2 sulphonyl groups and a fatty acid radical of approximately 8 to approximately 22 C atoms.
• alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate.
• suitable phosphates such as salts of the phosphoric ester of a p-nonylphenol/(4-14)ethylene oxide adduct, or phospholipids.
• the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of compound according to the present invention and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid carrier, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants (% in each case meaning percent by weight).
• surfactants % in each case meaning percent by weight.
• concentrated compositions tend to be preferred for commercial goods
• the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient.
• Example F1 Emulsion concentrates a) b) c) Active ingredient 25% 40% 50% Calcium dodecylbenzenesulfonate 5% 8% 6% Castor oil polyethylene glycol ether (36 mol of EO) 5% — — Tributylphenoxypolyethylene glycol ether (30 mol of EO) — 12% 4% Cyclohexanone — 15% 20% Xylene mixture 65% 25% 20% Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
• Example F2 Solutions a) b) c) d) Active ingredient 80% 10% 5% 95% Ethylene glycol monomethyl 20% — — — ether Polyethylene glycol — 70% — — MW 400 N-Methylpyrrolid-2-one — 20% — — Epoxidized coconut oil — — 1% 5% Petroleum ether — — 94% — (boiling range: 160-190°) The solutions are suitable for use in the form of microdrops.
• Example F3 Granules a) b) c) d) Active ingredient 5% 10% 8% 21% Kaolin 94% — 79% 54% Highly disperse silica 1% — 13% 7% Attapulgite — 90% — 18% The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier(s), and the solvent is subsequently evaporated in vacuo.
• Example F4 Dusts a) b) Active ingredient 2% 5% Highly disperse silica 1% 5% Talc 97% — Kaolin — 90% Ready-to-use dusts are obtained by intimately mixing the carriers and the active ingredient.
• Example F5 Wettable powders a) b) c) Active ingredient 25% 50% 75% Sodium lignosulfonate 5% 5% — Sodium lauryl sulfate 3% — 5% Sodium diisobutyl- — 6% 10% naphthalenesulfonate Octylphenoxypolyethylene glycol — 2% — ether (7-8 mol of EO) Highly disperse silica 5% 10% 10% Kaolin 62% 27% —
• the active ingredient is mixed with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders, which can be diluted with water to give suspensions of any desired concentration.
• Example F6 Extruder granules Active ingredient 10% Sodium lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 87% The active ingredient is mixed with the additives, and the mixture is ground, moistened with water, extruded, granulated and dried in a stream of air.
• Example F7 Coated granules Active ingredient 3% Polyethylene glycol (MW 200) 3% Kaolin 94% In a mixer, the finely ground active ingredient is applied uniformly to the kaolin, which has been moistened with the polyethylene glycol. This gives dust-free coated granules.
• Example F8 Suspension concentrate Active ingredient 40% Ethylene glycol 10% Nonylphenoxypolyethylene glycol ether (15 mol of EO) 6% Sodium lignosulfonate 10% Carboxymethylcellulose 1% 37% aqueous formaldehyde solution 0.2% Silicone oil (75% aqueous emulsion) 0.8% Water 32% The finely ground active ingredient is mixed intimately with the additives. Suspensions of any desired concentration can be prepared from the thus resulting suspension concentrate by dilution with water.
• Example F9 Powders for dry seed treatment a) b) c) active ingredient 25% 50% 75% light mineral oil 5% 5% 5% highly dispersed silicic acid 5% 5% — Kaolin 65% 40% — Talcum — — 20% The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
• Example F10 Emulsifiable concentrate active ingredient 10% octylphenol polyethylene glycol ether 3% (4-5 mol of ethylene oxide) calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether (35 mol of ethylene oxide) 4% Cyclohexanone 30% xylene mixture 50% Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.
• Example F11 Flowable concentrate for seed treatment active ingredients 40% propylene glycol 5% copolymer butanol PO/EO 2% Tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one 0.5% (in the form of a 20% solution in water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%
• the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
• foliar formulation types for pre-mix compositions are:
• examples of seed treatment formulation types for pre-mix compositions are:
• formulation types suitable for tank-mix compositions are solutions, dilute emulsions, suspensions, or a mixture thereof, and dusts.
• the methods of application such as foliar, drench, spraying, atomizing, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
• the tank-mix compositions are generally prepared by diluting with a solvent (for example, water) the one or more pre-mix compositions containing different pesticides, and optionally further auxiliaries.
• a solvent for example, water
• Suitable carriers and adjuvants can be solid or liquid and are the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
• a tank-mix formulation for foliar or soil application comprises 0.1 to 20%, especially 0.1 to 15%, of the desired ingredients, and 99.9 to 80%, especially 99.9 to 85%, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 20%, especially 0.1 to 15%, based on the tank-mix formulation.
• auxiliaries including, for example, a solvent such as water
• a pre-mix formulation for foliar application comprises 0.1 to 99.9%, especially 1 to 95%, of the desired ingredients, and 99.9 to 0.1%, especially 99 to 5%, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50%, especially 0.5 to 40%, based on the pre-mix formulation.
• a solid or liquid adjuvant including, for example, a solvent such as water
• a tank-mix formulation for seed treatment application comprises 0.25 to 80%, especially 1 to 75%, of the desired ingredients, and 99.75 to 20%, especially 99 to 25%, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 40%, especially 0.5 to 30%, based on the tank-mix formulation.
• auxiliaries including, for example, a solvent such as water
• a pre-mix formulation for seed treatment application comprises 0.5 to 99.9%, especially 1 to 95%, of the desired ingredients, and 99.5 to 0.1%, especially 99 to 5%, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50%, especially 0.5 to 40%, based on the pre-mix formulation.
• a solid or liquid adjuvant including, for example, a solvent such as water
• Preferred seed treatment pre-mix formulations are aqueous suspension concentrates.
• the formulation can be applied to the seeds using conventional treating techniques and machines, such as fluidized bed techniques, the roller mill method, rotostatic seed treaters, and drum coaters. Other methods, such as spouted beds may also be useful.
• the seeds may be presized before coating. After coating, the seeds are typically dried and then transferred to a sizing machine for sizing. Such procedures are known in the art.
• the pre-mix compositions of the invention contain 0.5 to 99.9 especially 1 to 95, advantageously 1 to 50, %, by mass of the desired ingredients, and 99.5 to 0.1, especially 99 to 5, %, by mass of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries (or adjuvant) can be a surfactant in an amount of 0 to 50, especially 0.5 to 40, %, by mass based on the mass of the pre-mix formulation.
• a solid or liquid adjuvant including, for example, a solvent such as water
• a compound of the formula (I) is in a preferred embodiment, independent of any other embodiments, is in the form of a plant propagation material treating (or protecting) composition, wherein said plant propagation material protecting composition comprises additionally a colouring agent.
• the plant propagation material protecting composition or mixture may also comprise at least one polymer from water-soluble and water-dispersible film-forming polymers that improve the adherence of the active ingredients to the treated plant propagation material, which polymer generally has an average molecular weight of at least 10,000 to about 100,000.
• combinations of the present invention i.e. those comprising a compound of the present invention and one or more other biological active agents
• the ingredients of a combination are applied sequentially (i.e., one after the other), the ingredients are applied sequentially within a reasonable period of each other to attain the biological performance, such as within a few hours or days.
• the order of applying the ingredients in the combination i.e., whether the compounds of formula (I) should be applied first or not is not essential for working the present invention.
• ingredients of the combinations may be applied as a composition containing the combination, in which case (A) the compound of formula (I) and the one or more other ingredients in the combinations can be obtained from separate formulation sources and mixed together (known as a tank-mix, ready-to-apply, spray broth, or slurry), or (B) the compound of formula (I) and the one or more other ingredients can be obtained as single formulation mixture source (known as a pre-mix, ready-mix, concentrate, or formulated product).
• A the compound of formula (I) and the one or more other ingredients in the combinations can be obtained from separate formulation sources and mixed together (known as a tank-mix, ready-to-apply, spray broth, or slurry), or
• B) the compound of formula (I) and the one or more other ingredients can be obtained as single formulation mixture source (known as a pre-mix, ready-mix, concentrate, or formulated product).
• a compound according to the present invention is applied as a combination. Accordingly, the present invention also provides a composition comprising a compound according the invention as herein described and one or more other biological active agents, and optionally one or more customary formulation auxiliaries; which may be in the form of a tank-mix or pre-mix composition.
• the combinations according to the invention also can have surprising advantageous properties which can also be described, in a wider sense, as synergistic activity.
• advantageous properties that may be mentioned are: advantageous behaviour during formulation and/or upon application, for example upon grinding, sieving, emulsifying, dissolving or dispensing; increased storage stability; improved stability to light; more advantageous degradability; improved toxicological and/or ecotoxicological behaviour; or any other advantages familiar to a person skilled in the art.
• the compounds of the present invention for use in agriculture is preferably as a nematicide.
• the compounds of the present invention may also find application in other fields, such as one or more of protection of stored goods and store rooms, the protection of raw materials (such as wood and textiles), floor coverings and buildings, and in hygiene management—especially the protection of humans, domestic animals and productive livestock against pests.
• the invention therefore also makes available pesticidal compositions for such uses and the methods therefor.
• the composition would need to be modified for use in a particular use, and a skilled person would be able to make available such compositions for any particular use.
• compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
• ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
• compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
• the compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes b Camillus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneu
• hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus augur , and termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus , and bristletails such as Lepisma saccharina.
• the invention also provides a method for treating, curing, controlling, preventing and protecting warm-blooded animals, including humans, and fish against infestation and infection by helminths, arachnids and arthropod endo- and ectoparasites which comprises orally, topically or parenterally administering or applying to said animals an anthelmintically, acaricidally or endo- or ectoparasiticidally effective amount of compound of formula (I).
• the above method is particularly useful for controlling and preventing helminth, nemtode, acarid and arthropod endo- and ectoparasitic infestations and infections in warm-blooded animals such as cattle, sheep, swine, camels, deer, horses, poultry, fish, rabbits, goats, mink, fox, chinchillas, dogs and cats as well as humans.
• warm-blooded animals such as cattle, sheep, swine, camels, deer, horses, poultry, fish, rabbits, goats, mink, fox, chinchillas, dogs and cats as well as humans.
• compounds of invention are especially useful for the control of helminths and nematodes.
• helminths are members of the class Trematoda, commonly known as flukes or flatworms, especially members of the genera Fasciola, Fascioloides, Paramphistomu, Dicrocoelium, Eurytrema, Ophisthorchis, Fasciolopsis, Echinostoma and Paragonimus .
• Nematodes which can be controlled by the formula (I) compounds include the genera Haemonchus, Ostertagia, Cooperia, Oesphagastomu, Nematodirus, Dictyocaulus, Trichuris, Dirofilaria, Ancyclostoma, Ascaria and the like.
• the compound of this invention may also control endoparasitic arthropod infestations such as cattle grub and stomach bot.
• acarid and arthropod ectoparasitic infestations in warm-blooded animals and fish including biting lice, sucking lice, bot flies, biting flies, muscoid flies, flies, myiasitic fly larvae, gnats, mosquitoes, fleas, mites, ticks, nasal bots, keds and chiggers may be controlled, prevented or eliminated by the compounds of this invention.
• Biting lice include members of Mallophaga such as Bovicola bovis, Trichodectes canis and Damilina ovis .
• Sucking lice include members of Anoplura such as Haematopinus eurysternus, Haematopinus suis, Linognathus vituli and Solenopotes capillatus .
• Biting flies include members of Haematobia .
• Ticks include Boophilus, Rhipicephalus, Ixodes, Hyalomma, Amblyomma and Dermacentor .
• the compounds of the invention may also be used to control mites which are parasitic on warm-blooded mammals and poultry including mites of the orders Acariformes and Parasitiformes.
• the compounds of the invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules.
• the compounds of the invention may be administered to the animals in their drinking water.
• the dosage form chosen should provide the animal with about 0.01 mg/kg to 100 g/kg of animal body weight per day of the compound of the invention.
• the compounds of the invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection.
• the compounds of the invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection.
• the compounds of the invention may be formulated into an implant for subcutaneous administration.
• the compounds of the invention may be transdermally administered to animals.
• the dosage form chosen should provide the animal with about 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compound of the invention.
• the compounds of the invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays and pour-on formulations.
• dips and sprays usually contain about 0.5 ppm to 5,000 ppm and preferably about 1 ppm to 3,000 ppm of the compound of the invention.
• the compounds of the invention may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
• the compounds of the invention may also be used in combination or conjunction with one or more other parasiticidal compounds (to broaden the spectrum of activity) including, but not limited to, anthelmintics, such as benzimidazoles, piperazine, levamisole, pyrantel, praziquantel and the like; endectocides such as avermectins, milbemycins and the like; ectoparasiticides such as arylpyrroles, organophosphates, carbamates, gamabutyric acid inhibitors including fipronil, pyrethroids, spinosads, imidacloprid and the like; insect growth regulators such as pyriproxyfen, cyromazine and the like; and chitin synthase inhibitors such as benzoylureas including flufenoxuron.
• anthelmintics such as benzimidazoles, piperazine, levamisole, pyrantel, pra
• the parasiticidal compositions of the present invention include a parasiticidally effective amount of a compound of the invention or combinations thereof admixed with one or more physiologically tolerable inert, solid or liquid carriers known from veterinary medicinal practice for oral, percutaneous and topical administration.
• Such compositions may comprise further additives, such as stabilizers, anifoams, viscosity regulators, binders and tackifiers, whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
• compositions according to the present invention may also be used for the preparation of composition useful to curatively or preventively treat human and animal fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.
• fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.
• a compound of formula (I) is a anti-helminth compound.
• a compound of formula (I) is a pesticidal compound, preferably a nematicidal compound.
• 2,6-difluorobenzoyl chloride (20 ml, 159.84 mmol) was added to a suspension of alpha-aminoisobutyric acid (7.417 g, 71.93 mmol) in pyridine (140 ml) under stirring at 0° C. The mixture was allowed to warm to room temperature and stirred for six days. The solvent was evaporated and the crude product mixture shaken between ether/hexane 1:4 and water. The organic phase was washed twice with HCl (1M), once with NaHCO 3 (1M), dried over Na 2 SO 4 , and evaporated to yield the product (14.3 g) as light yellow solid. M.p. 36-39° C.
• Step d Preparation of N-[1,1-dimethyl-2-oxo-2-[4-[trans-2-(trifluoromethyl)-1-cyclopropyl]phenyl]ethyl]-2,6-difluoro-benzamide (19.003)
• nBuLi in hexanes (19 ml, 1.6M, 30.2 mmol) was added slowly to a solution of 1-bromo-4[2-trans-(trifluoromethyl)-1-cyclopropyl]benzene from step 1 (8.00 g, 30.2 mmol) in THF (50 ml) at ⁇ 70° C. After 15 minutes this new aryl lithium solution was added by cannula to the solution described above. After 1 hour at ⁇ 70° C. NH 4 Cl (5M, 50 ml) was added, the mixture warmed to RT, and tBuOMe (150 ml) and water (100 ml) was added.
• Step a N-[1,1-dimethyl-2-oxo-2-(4-vinylphenyl)ethyl]-2,6-difluoro-benzamide
• Tributylvinyltin (912 mg) was added to a solution of N-[1,1-dimethyl-2-oxo-2-(4-bromophenyl)ethyl]-2,6-difluoro-benzamide (1 g) in toluene (50 ml). The solution was degassed and flushed with argon. Palladium(tetrakis(triphenylphosphine)) (302 mg) was added and the solution was stirred at 90° C. overnight then cooled to room temperature and quenched by addition of saturated aqueous sodium carbonate solution and stirred 4 hours at room temperature.
• Step b N-[1,1-dimethyl-2-oxo-2-[4-[2,2-dichlorocyclopropyl]phenyl]ethyl]-2,6-difluoro-benzamide (19.002)
• N-[1,1-dimethyl-2-oxo-2-(4-chlorophenyl)ethyl]-2,6-difluoro-benzamide (26 g) was dissolved in toluene (520 ml). Cyclopropyl boronic acid (10 g), tricyclohexylphosphine (2.16 g), potassium phosphate (57.2 g) and water (31 ml) were added followed by palladium acetate (0.86 g) and the solution was stirred at 100° C. overnight then cooled to room temperature and partitioned between water and ethyl acetate. The combined organic layers were washed with brine and the solvent was removed under reduced pressure. The crude residue was purified by flash chromatography (ethyl acetate/cyclohexane) to afford the title product as a dark yellow gum (48 g).
• Step a tert-Butyl (E)-3-[4-[2-[(2,6-difluorobenzoyl)amino]-2-methyl-propanoyl]phenyl]prop-2-enoate
• Step b trans-tert-Butyl-2-[4-[2-[(2,6-difluorobenzoyl)amino]-2-methyl-propanoyl]phenyl]cyclopropanecarboxylate (19.060)
• Step c trans-2-[4-[2-[(2,6-Difluorobenzoyl)amino]-2-methyl-propanoyl]phenyl]cyclopropane carboxylic acid (19.061)
• Step d trans-tert-Butyl N-[2-[4-[2-[(2,6-difluorobenzoyl)amino]-2-methyl-propanoyl]phenyl]cyclopropyl]carbamate (19.062)
• Step a 2,6-Difluoro-N-[2-(4-formylphenyl)-1,1-dimethyl-2-oxo-ethyl]benzamide
• N-[1,1-Dimethyl-2-oxo-2-(4-vinylphenyl)ethyl]-2,6-difluoro-benzamide (10.0 g, 30.4 mmol) was dissolved in CH 2 Cl 2 under argon. The solution was cooled to ⁇ 78° C. and ozone was blown through it, until it turned blue ( ⁇ 2 h). The reaction was quenched with dimethyl disulphide (0.1 ml) and warm up to RT overnight. Triphenylphosphine (1.0 g, 3.77 mmol) was then added to completely reduce the intermediate ozonide. Insoluble material was filtered off and the remaining solution was evaporated. The residue was purified by flash chromatography to give the title compound (5.67 g) as white crystals.
• Step b Ethyl 2-cyano-3-[4-[2-[(2,6-difluorobenzoyl)amino]-2-methyl-propanoyl]phenyl]prop-2-enoate
• Step c Ethyl 1-cyano-3-[4-[2-[(2,6-difluorobenzoyl)amino]-2-methyl-propanoyl]phenyl]-2,2-dimethyl-cyclopropanecarboxylate (20.001)
• Table 19 shows selected melting point, selected HPLC-MS, and selected NMR data for compounds of the present invention.
• CDCl 3 was used as the solvent for NMR measurements, unless otherwise stated. No attempt is made to list all characterising data in all cases.
• Table 20 contains another characterised compound 20.001 of the formula (IF)
• Heterodera schachtii (Sugar Beet Cyst Nematode)
• the tested application rate of each compound was 200 ppm. All solutions were brought to a concentration of 400 ppm, respectively, as they were subsequently diluted by adding the equivalent amount of water containing juvenile nematodes. After preparation of the suspensions, 1 ml of each suspension and concentration was transferred to 16-well assay plates with a total of three replicates per treatment. Approximately 500 juveniles of Heterodera schachtii were added in 1 ml of water to each well. Nematodes in water served as controls. The plates were placed in a dark box and stored at room temperature. Nematode paralysis was determined after 24 hours incubation at 25° C. in darkness. Nematodes that showed no movement were considered immotile.
• the pouches were incubated in a moist chamber for twelve days and watered regularly to maintain good filter paper moisture essential for the growing cucumber root system. After this period, the filter paper containing the germinated cucumber seedling was removed from the plastic pouch to assess the number of galls caused by Meloidogyne spp. per root system. Phytotoxicity was measured as a reduction of growth of the emerged cucumber seedling in comparison to the control.
• Coated tomato cv. Roter Gnom seeds were sown 0.5 to 1 cm deep in 45 ml pots filled with field soil. Then pots were infested with nematodes by pipetting 2000 eggs of Meloidogyne spp. within a 2 ml suspension on top of the seed. The seed hole was filled with soil hereafter. Assessment of phytotoxicity (in %) and root galling occurred 28 days after inoculation. The roots were washed free of soil debris and the gall index was assessed according to Zeck 1971 on a scale from 0 to 7. Seed treatment rate: 1 mg Al/seed
• Heterodera schachtii Sudgar Beet Cyst Nematode
• Impulse seeds were planted in 45 ml pots filled with field soil. Seven days after sowing pots were infested with 500 J2 of Heterodera schachtii within a 2 ml suspension in two holes to the left and right of the seedling. Assessment of nematode numbers per g of root occurred 10 days after inoculation. The upper plant part was cut off and the roots were washed free of soil debris. Nematodes within the roots were stained with acid fuchsin stain solution. Nematodes within the roots were quantified under a dissecting scope at 40 ⁇ . Seed treatment rate: 0.6 mg Al/seed The following compounds showed a greater than 80% reduction of nematode population compared to the untreated control: 19.003, 19.008, 19.010, 19.015, 19.017.

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• 2014
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